Recent advances in polymer/layered silicate

nanocomposites: an overview from science to

technology
M. Okamoto*
Polymer/layered silicate nanocomposites (PLSNCs) offer remarkably improved mechanical and
other properties with low inorganic filler loading. The major development in this field has been
carried out over the last one and a half decades. However, the authors are far from the goal in
terms of understanding the mechanisms of the enhancement effect in the nanocomposites.
Continued progress in nanoscale controlling and an improved understanding of the physico-
chemical phenomena at the nanometre scale have contributed to the rapid development of novel
PLSNCs. The present paper describes recent advances in PLSNCs with the primary focus on
these advances from basic science to technology.
Keywords: Nanocomposite, Layered silicate

Introduction focus on recent advances from basic science to

A decade of research has shown that nanostructured
materials have the potential to significantly impact
growth at every level of the world economy in the
twenty-first century. This new class of materials is now
being introduced in structural applications, such as gas
barrier film, flame retardant product and other load
bearing applications (see Table 1).1
Of particular interest is recently developed nanocom-
posites consisting of a polymer and layered silicate (LS),
because they often exhibit remarkably improved
mechanical and other properties2 when compared with
pure polymer or conventional composites (both micro
and macrocomposites). A primary progress in polymer/
layered silicate nanocomposites (PLSNCs), a nylon 6/LS
hybrid3 reported by Toyota Central Research &
Development Co. Inc. (TCRD), was successfully pre-
pared by in situ polymerisation of e-caprolactam in a
dispersion of montomorrillonite (MMT). The silicate
can be dispersed in liquid monomer or a solution of
monomer. It has also been possible to melt and mix
polymers with layered silicates, avoiding the use of
organic solvents. The latter method permits the use of
conventional processing techniques such as injection
moulding and extrusion.
Continued progress in nanoscale controlling and an
improved understanding of the physicochemical phe-
nomena at the nanometre scale have contributed to the
rapid development of novel PLSNCs. The present paper
describes current research on PLSNCs with the primary
Advanced Polymeric Materials Engineering, Graduate School of
Engineering, Toyota Technological Institute, 2121 Hisakata,
Tempaku, Nagoya 468 8511, Japan
*Corresponding author, email okamoto@toyota-ti.ac.jp
technology.
Historical point of view
Earlier attempts of preparing polymer/LS composites are
found in almost half a century old patent literatures.4,5 In
such cases, incorporation of 4050 wt-% clay mineral
(bentonite, hectorite, etc.) into a polymer was attempted
but ended up with unsatisfactory results: the maximal
modulus enhancement was only y200%, although the
clay loading was as much as 50 wt-%. The failure was
obvious, because they failed to achieve good dispersion of
clay particles in the matrix, in which silicate minerals
existed as agglomerated tactoids. Such a poor dispersion
of the silicate particles could improve the material
rigidity, but certainly sacrificing the strength, the elonga-
tion at break and the toughness of the materials.4,5
A major reason for this impossibility of improving the
tactoids dispersion into well dispersedexfoliated mono-
layers of the silicate is obviously due to the intrinsic
incompatibility of hydrophilic layered silicates with
hydrophobic engineering plastics. One attempt at
circumventing this difficulty was made by Unitika
Ltd.6 about 30 years ago in preparing nylon 6/LS
composites (not nanocomposites) via in situ polymerisa-
tion of e-caprolactam with MMT, but the results turned
out to be not very good.
The first major breakthrough of the problem was
brought about in 1987, when Fukushima and Inagaki of
TCRD, via their detailed study on polymer/LS compo-
sites, persuasively demonstrated that lipophilisation by
replacing inorganic cations in galleries of the native
clay with alkylammonium surfactant successfully made
them compatible with hydrophobic polymer matrixes.7
The modified clay was thus called lipophilised clay,
organophillic clay or simply organoclay. Furthermore,

2006 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 1 October 2005; accepted 28 November 2005
756 DOI 10.1179/174328406X101319 Materials Science and Technology 2006 VOL 22 NO 7

they found that the lipophilisation enabled to expand
silicate galleries and exfoliate the silicate layers into
single layers of a nanometre thickness.
Six years later, in 1993, Usuki, Fukushima and their
colleagues of TCRD successfully prepared, for the first
time, and exfoliated nylon 6/MMT hybrid via in situ
polymerisation of e-caprolactam, in which alkylam-
monium modified MMT was thoroughly dispersed in
advance.3,8
Apart from this, the intercalation of small molecules
into silicate galleries has been found by researchers when
studying Mayan archeological sites.9 Maya blue was
used in Mesoamerica and colonial Mexico as late as the
twentieth century. Maya blue colour is resistant to
diluted mineral acids, alkalis, moderate heat and even
biocorrosion. This blue colour contains clay (mainly
MMT clay and palygorskite (Mg5(Si,Al)8O20(OH)28H2O)
(see Table 2)) and indigo molecules (C16H10N2O2).
Intercalation of indigo molecules into MMT galleries
and/or encapsulation in the pores of palygorskite might
explain the corrosion resistance in the extreme condition
of the rain forest. Up to now, Maya blue paint has been
understood as an origin of the intercalation and recog-
nised as an ancient nanostructured materials (see Fig. 1).
Structure of layered silicates and its
modification
The commonly clays used for the preparation of PLSNCs
belong to the same general family of phyllosilicates. Their
Table 1 Thermoplastic olefin (TPO) nanocmposites: application for automotive parts*
HUMMER H2 SUT: most recent
nanocomposite application
Impala: the second nanocomposite application
*Through the courtesy of M. Verbrugge, General Motors.
Okamoto Recent advances in polymer/layered silicate nanocomposites
crystal structure consists of layers made up of two silica
tetrahedral fused to an edge shared octahedral sheet of
either aluminium or magnesium hydroxide. The layer
thickness is y1 nm and the lateral dimensions of these
layers may vary from 30 nm to several micrometres and
even larger depending on the particular layered silicate.
Stacking of the layers leads to a regular van der Waals
gap between the layers called the interlayer or gallery.
Isomorphic substitution within the layers (for example,
Alz3 replaced by Mgz2 or by Fez2, or Mgz2 replaced by
Liz1) generates negative charges that are counterba-
lanced by alkali and alkaline earth cations situated inside
the galleries, as shown in Fig. 2 and Table 2.
The most commonly used layered silicates are MMT
hectorite and saponite with different chemical formula
respectively, Mx(Al4-xMgx)Si8O20(OH)4, Mx(Mg6-xLix)-
Si8O20(OH)4 and Mx(Si8-xAlx)Si8O20(OH)4 (x50.51.2).
The type of clay is characterised by a moderate surface
charge cation exchange capacity (CEC of 80
120 mequiv/100 g) and layer morphology. These clays
are only compatible with hydrophilic polymers, such as
poly(ethyleneoxide) (PEO) and poly(vinylalcohol)
(PVA). To improve compatibility with other polymer
matrixes, one must convert the normally hydrophilic
silicate surface to organophilic, which makes possible
intercalation of many engineering polymers. Generally,
this can be carried out by ion exchange reactions with
cationic surfactants including primary, secondary,
tertiary and quaternary alkyl ammonium or alkylpho-
sphonium cations. The role of alkylammonium or
Nanocomposite TPOs summary of tangible benefits
Mass savings of 321%
$ Specific gravity of 0.92 versus 0.961.13 g cm23
$ Lighter weight reduces cost and requires less
adhesive for attachment
Improved appearance
$ Improved knit line appearance
$ Improved colourability and paintability
$ Sharper feature lines and grain patterns
$ Improved scratch/mar performance
Large processing window
$ Consistent physical and mechanical properties
$ Elimination/reduction of tiger striping
Reduced paint delamination
Retains low temperature ductility
Improved recyclability
Lower flammability
M-van step assist: the first commercial launch
Materials Science and Technology 2006 VOL 22 NO 7 757
Okamoto Recent advances in polymer/layered silicate nanocomposites

2 Structure of 2 : 1 phyllosilicates (montmorillonite)

alkylphosphonium cations in the organosilicates is to

1 a Maya blue was used in this mural representing soli-
der from Msoamerica and b needle shape of palygors-
kite crystals. Reprinted with permission from Ref. 9,
1996, American Association for the Advancement of
Science
Table 2 Clay mineral (phyllosilicates) classification
lower the surface energy of the inorganic host and
improve the wetting characteristics with the polymer
matrix, and results in a larger interlayer spacing. One
can evaluate a Naz density of 0.7 Naz/nm2, i.e. 7000
alkylammonium salt molecules are localised near the
individual silicate layers (about 1006100 nm2) and
active surface area (about 700900 m2 g21 as deter-
mined by BraunauerEmmettTeller (BET)). This result
indicates the organoclay platelets are hairy plates.
Furthermore, the surface hydroxyl concentration of

Type Group Groupoid Species Tetrahedron Octahedron Interlayer cation

2 : 1 Si4O10(OH)2 Pyrophyllite talc (x<0) di. Pyrophyllite Si4 Al2

tri. Talc Si4 Mg3
Smectite (0.25,x,0.6) di. Montmorillonite Si4 (Al2, Mg)2 Na, Ca, H2O
di. Hectorite Si4 (Mg2, Li)2 Na, Ca, H2O
di. Beidellite (Si, Al )4 Al2 Na, Ca, H2O
tri. Saponite (Si, Al )4 Mg3 Na, Ca, H2O
Vermiculite (0.25,x,0.9) di. Vermiculite (Si, Al )4 (Al, Mg)2 K, Al, H2O
tri. Vermiculite (Si, Al )4 (Mg, Al)3 K, Mg, H2O
Mica (x<1) di. Muscovite Si3?Al Al2 K
Paragonite Si3?Al Al2 Na
Brittle mica (x<2) tri. Phlogopite Si3?Al (Mg, Fe2z)3 K
Biotite Si3?Al (Fe2z, Mg)3 K
2 : 1 : 1 Si4O10(OH)8 Chlorite (large variation of x) di. Donbassite (Si, Al )4 Al2 Al2(OH)6
di.tri. Sudoite (Si, Al )4 (Al, Mg)2 (Mg, Al)3(OH)6
tri. Clinochlore (Si, Al )4 (Mg, Al)3 (Mg, Al)3(OH)6
Chamosite (Si, Al )4 (Fe, Al)3 (Fe, Al)3(OH)6
1 : 1 Si2O5(OH)4 Kaolin mineral serpentinite (x<0) di. Kaolinite Si2 Al2
Halloysite Si2 Al2 H2O
tri. Chrysotile Si2 Mg3
Needle Sepiolite palygorskite (x<0) tri. Sepiolite Si12 Mg8 (OH2)4?H2O
Palygorskite Si8 Mg8 (OH2)4?H2O
Amorphouslow crystalline Imogolite SiO3OH Al(OH)3
Allophane (12)SiO2?(56)H2O
Hisingerite SiO2Fe2O3H2O
x: degree of isomorphous substitution; di.: dioctahedral; tri.: trioctahedral.

758 Materials Science and Technology 2006 VOL 22 NO 7


3 Principle of repulsion of sheet like nanoparticles via
surface modification with bifunctional molecules.
Reprinted with permission from Ref. 17, 2003,
Elsevier Science
clays was determined by titration with triethyl alumi-
nium. Assuming that the hydroxyl groups are randomly
distributed on the edge surface, a SiOH density of 5 Si
OH/nm2 can be calculated,10 i.e. 500 OH groups are
localised near the edge surface of the individual silicate
layers (about 16100 nm2). This lipophilichydrophobic
balance is the key issue of the fine dispersion of the
organoclay platelets into the polymeric matrixes.
Additionally, the alkylammonium or alkylphosphonium
cations could provide functional groups that can react
with the polymer matrix or in some cases initiate the
polymerisation of monomers to improve the strength of
the interface between the inorganic and the polymer
matrix.11,12
Because the thermal degradation of many organophi-
lic clays occurs at temperature .200uC, clays with
enhanced thermal stability are desired. Recent
approach is polymerically modified clays.1316
Poly(diallylammonium) salt and oligomeric styrene
based ammonium salt have been prepared and used to
produce PLSNCs. More interesting idea of the intro-
duction of a repulsion of the single clay layers against
each other is reported by Fischer (see Fig. 3).17 The
cations located in between the clay platelets are ion
exchanged by one of the functional groups on these
organic molecules, e.g. an ammonium group, leaving
another functional group, which can be positively
or negatively charged, present on the clay layers.
4-amino-1-naphthalenesulphonic acid is one of the
candidates.
Nobel compounding process
Hasegawa and Usuki18 reported a novel compounding
process using the Naz-MMT slurry and demonstrated
preparation of a nylon 6 nanocomposite, where the
silicate layers exfoliated and homogeneously dispersed
at nanometre level. The most merit of this compounding
process is that the PLSNC consisted of nylon 6 and
Naz-MMT is prepared without any surfactants of the
clay minerals and additives. However, it is difficult to
prepare a completely exfoliated nanocomposite by this
method (see Fig. 4). Originally the perfect exfoliation of
the silicate platelets may not be impossible owing to the
strong interaction between hydroxylated edgeedge
groups, and the clay platelets are sometimes flocculated
in any polymer matrixes as reported by van Olphen19
Okamoto Recent advances in polymer/layered silicate nanocomposites
pump
clay slurry
Nylon 6 pellet
vapour
vent
melting clay compounding
zone zone
casing
zone
4 Schematic representation depicting compounding pro-
cess for preparing the nylon 6 nanocomposites using
clay slurry: nylon 6 was put into the extruder at
2 kg h21 and melted in melting zone; clay slurry was
pumped into cylinder of the extruder at 2 kg h21 and
compounded with melting nylon 6 in compounding
zone at 240250uC; screw rotation speed was
200 rev min21; residence time in cylinder was
y10 min; sealing zone was set by sealing ring to pre-
vent water back flow for hopper; water of slurry was
removed from vent by vacuum to obtain nanocompo-
sites. Reprinted with permission from Ref. 18 2003,
Elsevier Science
(see section on Flocculation control and modulus
enhancement).
Recently, an in situ polymerisation method used
supercritical CO2 (sc-CO2) as a processing aid to achieve
a uniform distribution in a PLSNC at high clay loading
(,40 wt-%).20 Zhao et al.21 presented unambiguous
evidence for sc-CO2 mediated intercalation of PEO into
NazMMT compared with polymer intercalation in
solution, in which an entropy driven process is
dominant. This mechanism is probably similar to that
in polymer melts. Therefore, the sc-CO2 mediated
intercalation is an enthalpically driven process, deriving
from a favourable intercalation between PEO and
MMT.
Nanostructure properties control
Intercalation during crystallisation and
confinement
Recently, Maiti et al.22 reported that in the polypropy-
lene/LS nanocomposites (PPCNs) at high crystallisation
temperature Tc>110uC, where the crystallisation rate is
low enough to solidify the system, the intercalation
should be anticipated in the melt state during crystal-
lisation. The driving force of the intercalation originates
from strong hydrophilic interaction between the maleic
anhydride (MA) group and the polar clay surfaces.23
With increasing Tc, the small peak and shoulder shift
toward the smaller angle region in the PPCNs, suggest-
ing that the extent of intercalation takes place with
crystallisation.22
Figure 5 shows the diffraction peak from the (001)
planes d(001) of the clay gallery quantitatively, as a
function of Tc, obtained from their respective Bragg
reflections. Here, in the case of PPCN2 (including
2 wt-% inorganic clay), the peak is not prominent. The
dotted line shows the effect of annealing on the d(001)
value of organoclay. The d(001) increases with Tc for both
PPCN4 and PPCN7.5 systems, and PPCN4 always
exhibits significantly higher value than PPCN7.5. This
implies that intercalation proceeds at Tc and increases
with decreasing clay content. Further decrease in clay
Materials Science and Technology 2006 VOL 22 NO 7 759
Okamoto Recent advances in polymer/layered silicate nanocomposites
5 Tc dependence of interlayer spacing of PPCN4 and
PPCN7.5: broken line shows annealing effect on orga-
noclay. Reprinted with permission from Ref. 22,
2002, American Chemical Society
content from 4 to 2 wt-% in PPCN2 leads to a partially
exfoliated system as discussed in the literature.23 That is,
the PPCN with low clay content crystallised at high Tc
(>110.0uC) exhibits higher amount of intercalation than
that with high clay content crystallised at any Tc.
At high Tc (>110uC) (low crystallisation rate), the
melt state exists for quite a long time and PPMA chains
have enough time to intercalate before crystallisation
can occur in the bulk. Then, the enhanced intercalation
is produced. The extent of intercalation is strongly
dependent on the time of the molten state. In other
words, the intercalated PPCNs are not equilibrated. By
decreasing the clay content in the nanocomposites, the
virtual gallery space in the silicate layers decreases and
consequently, the PPMA molecules would try to
accommodate, through interaction, in the minimum
space causing higher intercalated species. For
silicate layer of clay
PP molecule
stearyl ammonium
maleic anhydride group
6 Illustration of diffusion mechanism by suitable crystallisation. Reprinted with permission from Ref. 22, 2002,
American Chemical Society
760 Materials Science and Technology 2006 VOL 22 NO
sufficiently low clay content, a system, like PPCN2,
with less gallery space, is partially exfoliated owing to
high number density of tethering junction.
There are two possible ways of ordering of polymer
chains inside the silicate gallery by either polymer
molecules escape from gallery and crystallise outside
(diffuse out) or molecules may penetrate into the silicate
gallery when they are in the molten state (diffuse in).
When PPCN4 is directly crystallised from the melt at
70.0uC for two different times of 30 min and 17 h, the
interlayer spacing is the same (2.75 nm). If PPCN4 melt is
annealed at 150.0uC, just above melting temperature Tm
(145.0uC) for sufficiently long time and then subsequently
crystallised at 70.0uC for 30 min, the interlayer spacing
increases to 2.96 nm. Furthermore, when PPCN4 is
crystallised from the melt at 30uC, where crystallisation
rate is slow enough, the interlayer spacing becomes
3.08 nm. All these experiments indicate that the extent of
intercalation is strongly dependent on the time of the
molten state and ordering of polymer chains occurs
through a diffuse in mechanism. In other words, a slower
crystallisation rate makes a more intercalated species as
molten polymer molecules have sufficient time to diffuse
into the silicate gallery. Based on the wide angle X-ray
diffraction (WAXD) and TEM micrographs, the nature
of intercalation has been represented by Maiti and
Okamoto22,24 in Fig. 6. Therefore, by suitably crystal-
lising the PPCNs, the fine structure (confined orientation)
of the PLSNCs can be controlled.
According to Khares prediction,25 the confinement of
polymer chains increases the viscosity and mechanical
properties of the system significantly. Some difference in
mechanical properties with the change of the degree of
intercalation in the PPCNs vis-a-vis the clay content and
Tc can be expected (see Table 3). It is clear from Table 3
that for a particular Tc, the dynamic storage modulus G
increases with increasing clay content. The PPMA
crystallised at 130uC exhibits a 9.9% increase in G
compared with the sample crystallised at 70.0uC. The
PPCN7.5 and PPCN 4 show 13.3 and 30.6% increases
nt
Tc nte
low co
(1) cla
y
h
hig
(2)
(1) high Tc
(2) moderate clay content
low
clay
con
ten
t
7
 Okamoto Recent advances in polymer/layered silicate nanocomposites

2.8 2.5
2.6 L=200 nm L=200 nm m
(1)
d(001) 5n
increases
2.4 1n
m
d(001)=4 nm 2
2.2 dz=0.615 nm (2) dz=0.615 nm
Eeffective/Em=100 N=2 m
Eeffective/Em=100 5n
2
EII/Em

EII/Em
(3)
m
1.8 N decreases 1n
(4) d(001)
1.6 1.5 increases
N=5
1.4
1.2
(a) 1 1 (b)
0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10
Wc (%) Wc (%)

a effect of N at fixed d(001)54.0 nm; b effect of d(001) at two fixed values N52 and N55
7 Effect of clay structural parameters (N, d(001)) on macroscopic modulus predicted by Mori-Tanaka model. Reprinted
with permission from Ref. 26, 2004, Elsevier Science

respectively in the same condition. The effect of Tc on modulus of the PLSNC. The enhancement of modulus
the G is in the order of PPMA,PPCN7.5,PPCN4. It E11/Em is plotted as a fuction of clay content Wc and N
may be recalled that the Tc dependence of d(001) showed at fixed d(001). The strong dependence of modulus on N
the order of intercalation PPCN7.5,PPCN4 in Fig. 5. is cleary demonstrared; at a fixed Wc, modulus increases
This implies that much higher efficiency of the inter- with decreasing N; the amount of increase gradually
calation for the reinforcement is attained in the PPCN4. expands as NR1. On the other hand, the effect d(001) on
For PPCN2, owing to the partial exfoliation, the degree the modulus for two different values of N (N52 and 5).
of intercalation decreases, and hence the modulus Compared with N, the influence of d(001) on modulus is
decreases compared with the low Tc condition rather small and depends on the specific value of N. This
(570uC). Here, it should be mentioned that the crystal- increment is rather negligible when N is small, however,
linity increases little bit with increasing Tc for both PP when the nanocomposite is highly intercalated (e.g.
MA and PPCNs and the extent is almost the same for N55), the increase in a few nanometres in d(001) can
all the systems. Therefore, it is believed that not the cause a considerable increase in modulus.
crystallinity, but the degree of intercalation does affect In the case of nylon 6, the transcrystallisation
on the storage modulus. behaviour induced by the nanoclay is taken into account
by modelling a layer of matrix surrounding the particle to
Multiscale micromechanical modelling be highly textured and therefore mechanically anisotro-
Very recently, Sheng and Boyce26 reported a multiscale pic. Micromechanical models (numerical and analytical)
modelling strategy to account for the hierarchical based on the effective clay particle were employed to
morphology of the nanocomposite: at a lengthscale of calculate the overall elastic modulus of the amorphous
thousands of micrometres, the structure is one of high and semicrystalline PLSNCs and to compute their
aspect ratio particles within a matrix; at the lengthscale dependence on the matrix and clay properties as well as
of micrometres, the clay particle structure is either internal clay structural parameters. The proposed model-
exfoliated clay sheets of nanometre level thickness or ling technique captures the strong modulus enhancements
stacks of parallel clay sheets separated from each other observed in elastomer/clay nanocomposites as compared
by interlayer galleries of nanometre level height, and the with the moderate enhancements observed in glassy and
matrix, if semicrystalline, consists of fine lamella, semicrystalline PLSNCs. For the case where the matrix is
oriented with respect to the polymer/nanoclay interfaces. semicrystalline (like nylon 6), the proposed approach
Models of various representative volume elements of captures the effect of transcrystallised matrix layers in
the underlying structure of the clay filled polymer are terms of composite modulus enhancement, however, this
constructed. Figure 7 shows the influence of internal clay effect is found to be surprisingly minor in comparison
structural parameters (the average number of silicate with the composite level effects of stiff particles in a
layers per clay stack: N, d(001)) on the macroscopic matrix. This reason is discussed in Section Higher-order
structure development and crystallisation controlled by
Table 3 Dynamic storage modulus of PPMA and silicate surfaces.
PPCNs at T550uC crystallised at different Note that in order to determine the nanocomposite
temperatures22 modulus, the modulus of nanoclay of 400 GPa is
employed. Most of the nanocomposite researchers believe
System Tc, uC G, 61028 Pa Increase, %
that the nanoclay has a high modulus of 170 GPa.2
PPMA 70 2.92 9.9 However, this value is absolutely acceptable or not even
130 3.21 though in the case of monolayered clay sheet.
PPCN2 70 4.79
130 4.50
PPCN4 70 5.16 30.6 Flexibility of single clay layer
130 6.74 A large degree of flexibility of the monolayered clay
PPCN7.5 70 7.49 13.3 sheet is reported.27 Two transmission electron micro-
130 8.49
scope (TEM) images are evident (see Fig. 8). One arises

Materials Science and Technology 2006 VOL 22 NO 7 761

Okamoto Recent advances in polymer/layered silicate nanocomposites
a 2 wt-%MMT; b 4 wt-%MMT
8 Bright field TEM images of PPCNs: dark lines are
cross-sections of silicate layers and bright areas are
PPMA matrix. Reprinted with permission from Ref. 23,
2001, Elsevier Science
from the clay layers that appear as about 150200 nm
curved sheets. When viewed edge on as shown in
Fig. 8b, several 58 nm stacked sheets are apparent.
The curved nature of the sheet is observed, for it is well
known that smectite clay sheet have a large degree of
flexibility.27 Sato and Kawamura28 reported the study of
the flexibility of smectite clay minerals by molecular
dynamics (MD) simulations. They took into account the
quantitative understanding of the mechanical behaviour
of a single clay layer in a completely exfoliated state. The
repeating unit of a layer is taken to be a050.52 nm and
b050.902 nm with formula of 2Na1/3 Al2[Si11/3Al1/3]-
O10(OH)2, which corresponds to that of beidellite (see
Table 2). When the size of the basic cell (A59.3 nm,
B52.6 nm, and C55 nm) (A type cell) is reduced by 3
40% in the A direction, the stationary structure of a clay
layer is obtained as a curved sheet with a 2 : 1 smectite
type layer. In such curved state, the layer experiences an
external stress of 0.50.7 GPa. The layer structure of a
clay fractures when the size of the same basic cell is
9 Images (TEM) of N6CN3.7 crystallised at a 170 and b 210uC: black strip inside white part is clay. Reprinted with per-
mission from Ref. 32, 2003, Wiley-VCH
762 Materials Science and Technology 2006 VOL 22 NO
reduced by .40%. This value is much lower than that of
muscovite (,2 GPa) which is also reported by the same
authors.29 The simulation has also been performed by
reducing the size of the basic cell (A53.1 nm, B5
10.7 nm, and C55 nm) (B type) in the B direction. The
clay layer is found to be more flexible along the A
direction than along the B direction. When the micro-
scopic structure of a curved clay layer is examined, it is
concluded that the main origin of the flexibility lies in
the change of SiOSi angle in the silicate tetrahedral
sheets rather than in the change of bond lengths. These
simulation results agree with the atomic force micro-
scopy (AFM) observations.30
Higher order structure development and
crystallisation controlled by silicate surfaces
The formation of c form in presence of clay in nylon
6/LS nanocomposite is well known.31 The essential
difference between c form and a form is the molecular
packing; in the a form, hydrogen bondings are formed
between antiparallel chains, while the molecular chains
have to twist away from the zigzag planes to form the
hydrogen bonds among the parallel chains in c form
giving rise to lesser interchain interaction as compared
with a form.
The lamellar morphology and distribution of clay
particles in the nylon 6 nanocomposite (N6CN3.7)
(MMT53.7 wt-%), crystallised at 170 and 210.0uC,
have been reported by Okamoto and Maiti,32 as shown
in Fig. 9. The white strips (Fig. 9a) represent the discrete
lamellar pattern, and after a close look, a black clay
particle inside the lamella is clearly observed. In other
words, lamellar growth occurs on both sides of the clay
particles, i.e. the clay particles are sandwiched by the
formed lamellae. This is a unique observation of
lamellar orientation on the clay layers. In the semicrys-
talline polymer generally the stacked lamellar orienta-
tion takes place. Figure 9b shows the typical shish kebab
type of structure. The lamellar pattern at high Tc
(Fig. 9b) is somehow similar but along with the
sandwiched structure, branched lamellae are formed,
which are originated from the parent sandwiched
lamella. There are no clay particles found inside the
branch lamella, and the c phase having irregular chain
packing with distortion (c* phase) is formed as revealed
by wide angle X-ray diffraction (WAXD), by which one
7
 Okamoto Recent advances in polymer/layered silicate nanocomposites

10 Schematic view of nucleation and growth mechanism

in N6CN3.7. Reprinted with permission from Ref. 32,
2003, Wiley-VCH

can observe only in the case of high Tc crystallised

N6CN3.7. This epitaxial growth (c* phase) on the 11 Nanostructured network in nylon 12/LS nanocompo-
parent lamella forms the shish-kebab type of structure, site. Reprinted with permission from Ref. 36, 2001,
which virtually enhance the mechanical properties of the Elsevier Science
nanocomposites like a bone material which consists of
collagen fibrils reinforced with tiny mineral particles, a particles with the sandwiched and network (shish-kebab)
few nanometres in thickness.33 structure have a high function as microvoid initiation
From this sandwiched structure, the accurate deter- sites, which are necessary for high toughness during
mination of long spacing and lamellar thickness of deformation. Very recently, Fratzl et al.38 reported that
N6NC3.7 from small angle X-ray scattering (SAXS) is the mechanical behaviour of the collagen mineral
questionable.34,35 It has to be remembered that nylon 6 nanocomposite in bone depends crucially both on
has the highest capability of forming hydrogen bonding components, mineral and wet collagen, and on their
to form hydrogen bonded sheet. The pseudohexagonal interaction (see Fig. 12).
packing is favoured with the hydrogen bonding between
the silicate layers and nylon 6, as a result the induction
time of N6CN3.7 becomes very short, as compared with
neat nylon 6. Once one molecular layer is nucleated on
the clay surface, other molecules may form the hydrogen
bonding on the already formed hydrogen bonded
molecule to the silicate surface giving rise to the discrete
lamellar structure on both sides of the clay. The
nucleation and growth process have been demonstrated
in Fig. 10, following direct observation by TEM.32 This
unique mechanism can well explain the higher crystal-
lisation rate of PLSNCs along with morphology and
developed internal structure. This sandwiched structure
(each silicate layer is strongly covered by polymer
crystals) makes the system very rigid, as a result the
heat distortion temperature (HDT) increases up to 80uC,
but the surrounding excess amorphous part (lower
crystallinity of N6CN3.7 as compared with neat nylon
6) can easily retain the polymeric properties like impact
strength, ultimately makes a improved/perfect system in
PLSNCs.
Kim and Kressler36 also reported that the fine
lamellae of nylon 12 crystals are oriented perpendicu- 12 Schematic arrangement of mineral and organic phase
larly to the nylon 12/LS interface, i.e. on planes lying in mineralised collagen fibril subjected to tensile load:
normal to the injection moulding direction. This mineral particles are shown in dark gray and should be
interfacial ordering may be a result of the crystallisation imagined as platelets viewed edge on; horizontal white
process and similar to the well known transcrystallisa- lines in light gray matrix (left part in figure) are not indi-
tion.37 The nanocomposites consist of a nanostructured cating any physical reality; they are just drawn to visua-
network finely dispersed and uniformly oriented silicate lise shear deformation in matrix between particles as
layers are aligned perpendicular to lamellae, and the consequence of tensile deformation of tissue (right
two materials are strongly bonded to each other (see part of figure). Reprinted with permission from Ref. 38,
Fig. 11). In these nylon nanocomposites, the nanoclay 2004, The Royal Society of Chemistry

Materials Science and Technology 2006 VOL 22 NO 7 763

Okamoto Recent advances in polymer/layered silicate nanocomposites
13 Stressstrain curves for neat PVDF (a phase crystal-
lite), PVDFNCU (microcomposite by MMT) and
PVDFNCM (nanocomposite by organoclay) showing
dramatic increase in elongation at break for
nanocomposite. Reprinted with permission from
Ref. 40, 2004, Wiley-VCH
In the case of polyvinylidene (PVDF)/LS nanocom-
posites, the formation of b form has been observed.39,40
Shah et al.40 reported a remarkable order of magnitude
enhancement in toughness of the nanocomposites (see
Fig. 13). They postulated that nucleation of the fiber like
b phase (more ductile than the a phase) on the surface of
individual silicate layers leads to a structure conductive
to plastic flow under applied stress. Energy dissipation
could be further enhanced owing to the presence of more
mobile b crystallites which have a potential of acting like
rigid fillers surrounded by the crystalline phase of
PVDF. Therefore, the crystallisation controlled by
silicate surfaces may provide not only a new approach
for toughening of polymers but also the way towards a
novel approach for the design of new materials.
In the case of polyester systems, Yamada et al.41
examined the HDT of various polylactide (PLA)/LS
nanocomposites (PLACNs) with different load condi-
tions. In the case of PLACN (MMT55 wt-%), there is
marked increase in HDT with intermediate load of
0.98 MPa, from 76uC for the neat PLA up to 111uC for
PLACN (see Fig. 14). In the case of high load
14 a Organoclay (wt-%) dependence of HDT of neat PLA and various PLACNs and b load dependence of HDT of neat
PLA and PLACN7. Reprinted with permission from Ref. 41, 2003, Elsevier Science
764 Materials Science and Technology 2006 VOL 22 NO
(1.81 MPa), however, it is very difficult to achieve high
HDT enhancement without strong interaction between
polymer matrix and organoclay like nylon systems.32
Therefore, the improvement of HDT with intermediate
load (0.98 MPa) originates from the better mechanical
stability of the PLACNs owing to mechanical reinforce-
ment by the dispersed clay particles and higher value of
the degree of crystallinity xc and intercalation. This is
qualitatively different from the behaviour of nylon
systems, where the MMT layers stabilise in a different
crystalline phase (c phase)32 with the strong hydrogen
bondings between the silicate layers and nylon 6, as a
result the discrete lamellar structure on both sides of the
clay (see Figs. 9 and 10). Nylon/LS nanocomposites are
successfully prepared without strategy for designing of
materials with desired properties of the PLSNCs.
Flocculation control and modulus enhancement
Most of the nanocomposite researchers obdurately
believe that the preparation of completely exfoliated
structure is the ultimate target for better overall
properties. However, these significant improvements
are not observed in every nanocomposite systems,
including systems where the silicate layers are near to
exfoliated.42 While from the barrier property stand-
point, the development of exfoliated nanocomposites is
always preferred. On the other hand, Nylon/LS nano-
composite systems are completely different from other
nanocomposite systems as discussed before.
In Fig. 15, Okamoto summarised the clay content
dependence of dynamic storage modulus G of various
types of nanocomposites obtained under well below Tg
of the matrixes. Einstein coefficient kE derived by Halpin
and Tais theoretical expression modified by Nielsen
is shown in Fig. 15, and represents the aspect ratio
Lclay/dclay of dispersed clay particles without inter-
calation. From Fig. 15, it is clearly observed that
poly(butylene succinate)(PBS)/LS nanocomposites
(PBSCNs) show very high increment in G compared
with other nanocomposites with the same content of
clay in the matrix. PPCNs are well known for
intercalated systems, N6CNs are well established exfo-
liated nanocomposites, PLACNs are going to establish
intercalated and flocculated nanocomposites, while
PBSCNs are intercalated and extended flocculated
nanocomposites systems.43,44 Owing to the strong
7

15 Plots of G9nanocomposite/G9matrix versus vol.-% of clay
for various nanocomposites: Einstein coefficient kE is
shown with number in box; lines show calculated
results from Halpin and Tais theory with various kE
interaction between hydroxylated edgeedge groups, as
above mentioned, the clay particles are some time
flocculated in the polymer matrix. As a result of this
flocculation the length of the clay particles increases
enormously and hence overall aspect ratio. For the
preparation of high molecular weights PBS, di-
isocyanate [OCN-(C6H12)-NCO] type end groups are
generally used as a chain extender. These isocyanate end
groups chain extender make urethane bonds with
hrydroxy terminated low molecular weight PBS, and
each high molecular weights PBS chain contain two such
kind of bonds (see Fig. 16). These urethane type bonds
lead to the strong interaction with silicate surface by
forming hydrogen bonds and hence strong flocculation
(see Fig. 17). For this reason, the aspect ratio of
dispersed clay particles is much higher in the case of
PBSCNs compared to all nanocomposites, and hence
high enhancement of modulus.
This behaviour with the help of classical rheological
theory of suspension of conventional filler reinforced
systems can be explained. According to this theory,45 the
rotation of filler is possible when volume fraction of clay
wfiller,wcritical>(aspect ratio)21. All PBSCNs studied
here follow this relation except PBSCN4 (MMT5
3.6 wt-%), in which wfiller&(aspect ratio)21. For this
reason in PBSCN4 rotation of dispersed intercalated
with flocculated stacked silicate layers is completely
17 Formation of hydrogen bonds between PBS and clay, which leads to flocculation of dispersed silicate layers.
Reprinted with permission from Ref. 43, 2003, American Chemical Society
Okamoto Recent advances in polymer/layered silicate nanocomposites
16 Formation of urethane bondings in high molecular
weight PBS
hindered and only translational motion is available, and
hence show very high modulus. This behaviour is clearly
observed in dynamic storage modulus measurements
under molten state.43 In the case of N6CN3.7 (MMT5
3.7 wt-%) the same high increment in G9 as well as
PBSCNs can be seen. The development of the floccu-
lated structure is occurred, even though N6CNs are well
established exfoliated nanocomposite systems.
Flow induced structure development
Steady shear flow
The steady shear rheological behaviour of neat PBS and
various PBSCNs are shown in Fig. 18. The steady
viscosity of PBSCNs is enhanced considerably at all
shear rates with time, and increases monotonically with
increasing silicate loading at a fixed shear rate.44 On the
other hand, all intercalated PBSCNs exhibit strong
rheopexy behaviour, and this becomes prominent at low
shear rates, while neat PBS exhibits a time independent
viscosity at all shear rates. With increasing shear rates,
the shear viscosity attains plateau after certain time, and
the time required to attain this plateau decreases with
increasing shear rates. The possible reasons for this type
of behaviour may be due to the planer alignment of the
clay particles towards the flow direction under shear.
When the shear rate is very slow (0.001 s21), clay
particles take longer time to attain complete planer
alignment along the flow direction, and this measure-
ment time (1000 s) is too short to attain such alignment
and hence show strong rheopexy behaviour. On the
other hand, at high shear rates (0.005 or 0.01 s21) this
measurement time is considerable enough to attain such
alignment, and hence, nanocomposites show time
independent shear viscosity after certain time.
Figure 19 shows shear rates dependence of viscosity
for neat PBS and corresponding nanocomposites
measured at 120uC. While the neat PBS exhibits almost
Newtonian behaviour at all shear rates, whereas
Materials Science and Technology 2006 VOL 22 NO 7 765
Okamoto Recent advances in polymer/layered silicate nanocomposites
18 Time variation of shear viscosity for PBSCN.
Reprinted with permission from Ref. 43, 2003,
American Chemical Society
nanocomposite exhibits non-Newtonian behaviour. At
very low shear rates, shear viscosity of nanocomposites
initially exhibits some shear thickening behaviour and
this is corresponding to the rheopexy behaviour
observed at very low shear rates (see Fig. 18). After
that all nanocomposites show very strong shear thinning
behaviour at all shear rates and this behaviour is
analogous to the results obtained in the case of dynamic
oscillatory shear measurements.41 Additionally, at very
high shear rates, the viscosities of nanocomposites are
comparable with that of neat PBS. These observations
suggest that the silicate layers are strongly oriented
towards the flow direction at high shear rates, and shear
thinning behaviour at high shear rates dominated by
that of neat polymer.
The PLSNC melts always exhibit significant deviation
from Cox-Merz relation,46 while all neat polymers nicely
obey the empirical Cox-Merz relation, which requires
: :
that for c5v, the viscoelastic data should obey the
766 Materials Science and Technology 2006 VOL 22 NO
19 Shear viscosity as function of shear rates for shear
rate sweep test. Reprinted with permission from
Ref. 43, 2003, American Chemical Society
:
relationship g(c)~jg
j(v). It is believed that there are
two possible reasons for the deviation of Cox-Merz
relation in the case of nanocomposites. First of all, this
rule is only applicable for homogenous systems like
homopolymer melts, but nanocomposites are hetero-
geneous systems. For this reasons this relation is nicely
obeyed in the case of neat polymer.43 Second, the
structure formation is different when nanocomposites
are subjected to dynamic oscillatory shear and steady
shear measurements.
Okamoto et al.47 constructed unique rheo-optical
device, angle light scattering apparatus (Rheo-SALS),
which enables the authors to perform time resolved
measurements of light intensity scattered from the
internal structure developed under shear flow.
Figure 20 shows a schematic illustration of the appara-
tus: plane polarised light normal to the x axis (flow
direction) was applied vertically to the parallel plate type
shear cell along the velocity gradient (y axis). Scattering
profiles were observed either under Vv mode (depo-
larised geometry in which the optical axis of the analyser
was set parallel to that of the polariser) or Hv (the cross-
polarised geometry with the two axes being set per-
pendicular to two axes) optical alignment at azimuthal
angle m of 0u. They reported the time variation of the
mean square density fluctuation ,g2., the mean square
anisotropy ,d2. and the relevant value of correlation
distance (jg and jd) upon imposition/cessation of steady
:
shear flow at both low shear rate c (>0.5 s21) and high
: 21
shear rate c (>60 s ).
Elongational flow and strain induced hardening
Okamoto et al.48 first conducted elongation test of PP/
LS nanocomposites (PPCN4) under molten state at
:
constant Hencky strain rate, e0 using an elongation flow
49
optorheometry and also they attempted to control the
alignment of the dispersed silicate layers with nanometre
dimensions of an intercalated PPCNs under uniaxial
elongational flow.
Figure 21 shows double logarithmic plots of transient
:
elongational viscosity gE (e0 ; t) against time t observed
for nylon 6/LS system (N6CN3.7) and PPCN4 (MMT5
:
4 wt-%) with different Hencky strain rates e0 ranging
from 0.001 to 1.0 s . The solid curve represents time
21
development of threefold shear viscosity 3g0 (c; t) at
7

a cross-sectional; b top views
20 Schematic illustration of Rheo-SALS apparatus.
Reprinted with permission from Ref. 47, 2000, The
Society of Rheology, Japan
: longer) examined here. This time dependent thickening
225uC with a constant shear rate c50.001 s21. In
: :
gE (e0 ; t) at any e0 , N6CN3.7 melt shows a weak
tendency of strain induced hardening as compared
with that of PPCN4 melt. A strong behaviour of
strain induced hardening for PPCN4 melt was origi-
nated from the perpendicular alignment of the silicate
layers to the stretching direction as reported by
Okamoto et al.48
From TEM observation (see Fig. 9), the N6CN3.7
forms a fine dispersion of the silicate layers of y100 nm
in Lclay, 3 nm thickness in dclay and jclay of about 20
30 nm between them. The jclay value is a one order of
magnitude lower than the value of Lclay, suggesting the
formation of spatially linked like structure of the dis-
persed clay particles in nylon 6 matrix. For N6CN3.7
melt, the silicate layers are so densely dispersed into the
matrix and hence difficult to align under elongational
flow. Under flow fields, the silicate layers might
translationally move, but not rotationally in such a
way that the loss energy becomes minimum. This
tendency was also observed in PPCN7.5 melt with
higher content of MMT57.5 wt-%.50
On the other hand, two features for the shear viscosity
curve can be observed. First, the extended Trouton rule
: :
3g0 (c; t)%gE (e0 ; t) does not hold for both N6CN3.7 and
PPCN4 melts, as opposed to the melt of ordinary
:
homopolymers. The latter gE (e0 ; t) is more than 10 times
:
larger than the former 3g0 (c; t). Second, again unlike
:
ordinary polymer melts, 3g0 (c; t) of N6CN3.7 melt
increases continuously with t, never showing a tendency
of reaching a steady state within the time span (600 s or
Okamoto Recent advances in polymer/layered silicate nanocomposites
21 Time variation of elongational viscosity gE(e0; t) for a
N6CN3.7 melt at 225uC and for b PPCN4 at 150uC:
solid line shows three times shear viscosity 3g0(c0; t),
taken at low shear rate c50.001 s21 on cone plate
rheometer. Reprinted with permission from Ref. 2,
2003, Rapra Technology Ltd
behaviour may be called antithixotropy or rheopexy. At
: :
slow shear flow (c 50.001 s21), 3g0 (c; t) of N6CN3.7
exhibits a much stronger rheopexy behaviour with
almost two order of magnitude higher than that of
PPCN4. This reflects a fact that the shear induced
structural change involved a process with an extremely
long relaxation time as well as for other PLSNCs with
rheopexy behaviour,43 especially under weak shear field.
Alignment of silicate layers
The orientation of silicate layers and nylon 6 crystallites
in injection moulded N6CN is examined using WAXD
and TEM.51,52 Kojima and his colleagues have found
three regions of different orientations in the sample as a
function of depth. Near the middle of the sample, where
the shear forces are minimal, the silicate layers are
oriented randomly and the nylon 6 crystallites are
perpendicular to the silicate layers. In the surface region,
shear stresses are very high, and therefore both the clay
layers and the nylon 6 crystallites are parallel to the
surface. In the intermediate region, the clay layers,
presumably owing to their higher aspect ratio, still orient
parallel to the surface and the nylon 6 crystallites assume
an orientation perpendicular to the silicate. Very
recently, Medellin-Rodriguez et al.53 reported that the
molten N6CN samples showed planar orientation of
silicate layers along the flow direction, which is strongly
dependent on shear time as well as clay loading,
reaching a maximally orienting level after being sheared
:
for 15 min with c560 s21.
Materials Science and Technology 2006 VOL 22 NO 7 767
Okamoto Recent advances in polymer/layered silicate nanocomposites
22 Micrograph (TEM) in xz plane showing N6CN3.7
sheared at 225uC with c50.0006 s21 for 1000 s: x, y
and z axes correspond to flow, shear gradient and
neutral direction respectively. Reprinted with permis-
sion from Ref. 2, 2003, Rapra Technology Ltd
Okamoto and his colleagues conducted the TEM
:
observation for the sheared N6CN3.7 with c5
0.0006 s for 1000 s (Ref. 2). The edges of the silicate
21
layers laying along the z axis (marked with the arrow
(a)) or parallel alignment of the silicate edges to the
shear direction (x axis) (marked with the arrow (b))
rather than assumingly random orientation in the nylon
6 matrix is observed, but in fact, these faces in this plane
can be seen (Fig. 22). Here, it should be emphasised that
the planar orientation of the silicate faces along the xz
plane does not take place prominently. For the case of
rapid shear flow, the commonly applicable conjecture of
the planar orientation of the silicate faces along the
shear direction first demonstrated to be true by Kojima
and his colleagues.51
In uniaxial elongational flow (converging low) for a
PPCN4, the formation of a house of cards structure is
found by TEM analysis.48 The perpendicular (but not
parallel) alignment of disk like clay particles with large
anisotropy towards the flow direction might sound
unlikely, but this could be the case especially under an
elongational flow field, in which the extentional flow rate
is the square of the converging flow rate along the
thickness direction, if the assumption of affine deforma-
tion without volume change is valid. Obviously under
such conditions, energy dissipation rate owing to viscous
resistance between the disk surface and the matrix
polymer is minimal, when the disks are aligned
perpendicular to the flow direction.
Moreover, Lele and his colleagues54 recently reported
the in situ Rheo X-ray investigation of flow induced
orientation in syndiotactic PP/layered silicate nanocom-
posite melt.
768 Materials Science and Technology 2006 VOL 22 NO
23 2D SAXS (a and c) and WAXS (b and d) patterns for
orientation MN (left face), NT (right face) and MT (top
face) of films HD603 (a and b) and HD612 (c and d):
numbers in parentheses represent reflections from
following: (a) clay tactoids, (b) modified/intercalated
clay (002) plane, (c) unmodified clay (002) plane, (d)
clay (110) and (020) plane, (e) polymer crystalline
lamellar, (f) polymer unit cell (110) plane (inner ring)
and (200) plane (outer ring). Reprinted with permis-
sion from Ref. 55, 2003, Elsevier Science
Very recently, Bafna et al.55 developed a technique to
determine the three-dimensional (3D) orientation of
various hierarchical organic and inorganic structures in
a PLSNCs. They studied the effect of compatibiliser
concentration on the orientation of various structures in
PLSNCs using two-dimensional (2D) SAXS and 2D
WAXD in three sample/camera orientations. Reflections
and orientation of six different structural features were
easily identified:
(i) clay clusters/tactoids (0.12 mm)
(ii) modified/intercalated clay stacking period (002)
(2.43.1 nm)
(iii) stacking period of unmodified clay platelets
(002) (1.3 nm)
(iv) clay (110) and (020) planes, normal (ii) and (iii)
(v) polymer crystalline lamellae (001) (1926 nm),
long period ((001) is an average crystallographic
direction)
(vi) polymer unit cell (110) and (200) planes.
The corresponding identified reflections are presented
in Fig. 23. A 3D study of the relative orientation of
the above mentioned structures was carried out by
measuring three projections of each sample.
Quantitative data on the orientation of these structural
units in the nanocomposite film were determined
through calculations of the major axis direction cosines
and through a ternary, direction cosine plot called a
Wilchinsky triangle,56 previously proposed in lamellar
orientation studies.57 It allows a direct comparison of
average preferred orientations for different structural
features. In this way it is conceptually more useful than
stereographic projections involving orientation density
maps for a single WAXD reflection.
7
 Okamoto Recent advances in polymer/layered silicate nanocomposites

About 20 years ago, van Olphen19 pointed out that
the electrostatic attraction between the layers of natural
clay in aqueous suspension arises from higher polar
force in the medium. The intriguing features such as
yield stress thixotropy and/or rheopexy exhibited in
aqueous suspensions of natural clay minerals may be
taken as a reference to the present PLSNCs.
For example, the strong strain induced hardening in
:
gE (e0 ; t) is requisite for withstanding the stretching force
:
during the processing, while the rheopexy in 3g0 (c; t)
suggests that for such PLSNC a promising technology is
the processing in confined space such the injection
moulding where shear force is crucial.

Electrorheology Foam processing using sc-CO2

Very recently, the first successful nanocomposite foam,
Electrorheological fluids (ERFs), sometimes referred to
processed by sc-CO2 as a physical foaming agent,
as smart fluids, are suspensions consisting of polari-
appeared through a pioneering effort by Okamoto and
sable particles dispersed in insulating media. A mis-
his colleagues.62,63
match in conductivity or dielectric constant between the
Figure 24 shows the typical results of SEM images of
dispersed particle and the continuous medium phase
the fracture surfaces of the intercalated polycarbonate
induces polarisation upon application of an electric filed.
(PC)/layered silicate nanocomposites (PCCNs) and PC/
The induced particle dipoles under the action of an
SMA blend (matrix) without clay foamed at 160uC
electric field tend to attract neighbouring particles and
under different isobaric saturation conditions of sc-CO2
cause the particles to form fibril like structures, which
(10, 14 and 18 MPa).64 PC/SMA foams exhibit the
are aligned to the electric field direction.
polygon closed cell structures with pentagonal and
Among various materials,5861 semiconducting poly-
hexagonal faces, which express the most energetically
mers are one of the novel intrinsic ER systems, because
stable state of polygon cells. Such foam structure was
it has the advantage of a wide range of working
obtained probably because these foams belong to the
temperature, reduced abrasion of device, low cost and
polymeric foams with high gas phase volume (.0.6).65
relatively low current density. As a result, development
Obviously, under low saturation CO2 pressure
of a high performance ERF followed by conducting
(,10 MPa), both PCCN foams exhibit large cell size,
polymer optimisation and tuning has been the subject of
indicating the dispersed clay particles hinder CO2
considerable interest for practical applications as a new
diffusion by creating a maze or a more tortuous path
electromechanic interface. Nevertheless, the yield stress
as discussed in the literatures.2 However, a high CO2
and modulus of ERFs are lower than those of
pressure (,18 MPa) provides a large supply of CO2
magnetorheological fluids. Therefore, the performance
molecules, which can subsequently form a large popula-
of conducting polymer based ERFs is still insufficient
tion of cell nuclei upon depressurisation. The PC/SMA/
for the successful development of specific application
MAE1 (2C12C18-fluorohectrite) (including organoclay
devices.
of 1 wt-%) foam shows smaller cell size, i.e. larger cell
On this basis of this informations, Kim et al.58 first
density compared with PC/SMA foam, suggesting that
introduced nanocomposite as ERFs using polyaniline
the dispersed clay particles act as nucleating sites for cell
(PANI)/LS nanocomposites with intercalated structure.
formation and lowering of d with clay. The incorpora-
Although PANI/clay intercalated nanocomposites are a
tion of nanoclay hinder CO2 diffusion and simulta-
new material for application of ER materials, yield
neously induce heterogeneous nucleation because of a
stresses of the system showed less than 100 Pa at
lower activation energy barrier compared with homo-
1.2 kV mm21 (20 wt-% suspensions). This value is a
geneous nucleation.66 They conducted the characterisa-
little lower than the yield stress of pure PANI particle
tion of the interfacial tension between bubble and matrix
system.59 In other words, no synergistic effect of clay on
by modified classical nucleation theory.66
yield stress was shown.
In Table 4, the interfacial tension of the systems is
Recently, Park and his colleagues60 have observed
summarised.67 It can be seen that PC/SMA system has a
remarkable enhancement of yield stress for ERFs in
slightly large value (17.3 mJ m22) compared with that of
PANI based nanocomposites of clay. In their further
PC/SMA/MAE1 (14.6 mJ m22) and PC/SMA/MTE1
study61, they fabricated three kinds of ERFs containing
(C13C8-fluorohectrite) (16.0 mJ m22) in the case of a
different contents of PANI/clay nanocomposite and
low CO2 pressure (10 MPa). These estimated values of c
pure PANI particles in order to investigate the effect of
are in good agreement with that of other poly(methyl-
nanocomposite particles on the enhancement of yield
methacrylate) (PMMA)CO2 system (1020 mJ m22).68
stress more systematically. They observed that there is
The value for PC/SMA system decreases with increasing
an optimum content ratio between nanocomposite and
CO2 pressure, as expected, while PC/SMA/MAE1 shows
pure PANI particles to produce minimum yield stress.
a constant value with increasing pressure. This trend
Details regarding data collection and explanations are
reflects the relative importance of heterogeneous
presented.61
Table 4 Interfacial tension of systems calculated using
Processing operations Suh and Coltons theory
The flow induced internal structural change occurs in System PCO2, MPa c, mJ m22
both shear and elongational flow, but almost differs
from each other, as judged from the above results on PC/SMACO2 10 17.3
: :
gE (e0 ; t) and 3g0 (c; t) (see Fig. 21). Therefore, with these PC/SMA/MAECO2 10 14.6
rheological features of the PCNs and the characteristics PC/SMA/MTECO2 10 16.0
of each processing operation, which process type should MAE: dimethyl dioctadecyl ammonium cation modified synthetic
be selected for a particular nanocomposite for the fluorohectorite; MTE: methyl trioctil ammonium cation modified
enhancement of its mechanical properties? synthetic fluorohectorite.

Materials Science and Technology 2006 VOL 22 NO 7 769

Okamoto Recent advances in polymer/layered silicate nanocomposites
24 Typical SEM images of fracture surfaces of PCCNs and PC/SMA blend without clay foamed at 160uC under different
isobaric conditions (10, 14 and 18 MPa)
nucleation, which dominates over homogeneous one in
the event that the amount of CO2 available for bubble
nucleation is limited.
Figure 25 shows the stressstrain curves and the strain
recovery behaviour of the PPCN foams62 in the com-
pression mode at a constant strain rate of 5% min21.
The nanocomposite foams exhibit high modulus com-
pared with neat PPMA foam. The residual strain is
17% for PPCN2 (including 2 wt-% of organoclay) as
well as neat PP foam, providing the excellent strain
recovery and the energy dissipation mechanism, prob-
ably with the house of cards structure formation in the
cell wall,62 which enhance the mechanical properties of
the nanocomposites like a spruce wood which is close to
right handed helix (see Fig. 26).63
25 Stressstrain curves and strain recovery behaviour of
PPCNs
770 Materials Science and Technology 2006 VOL 22 NO
Figure 27 shows the relationship among the cell size d,
the cell density Nc and the mean cell wall thickness d of
the nanocomposite foams obtained by a series of their
recent studies.64,69 In the case of nanocomposite foams,
the cell wall thickness becomes 26 times compared with
that of neat polymer foams owing to the spherical cell
shape63 caused by the high modulus of the materials
during processing. The controlled structure of the nano-
composite foams changes from microcellular (d>20 mm
and Nc>1.06109 cell cm23) to nanocellular (d>200 nm
and Nc>1.061014 cell cm23).
26 X-ray microdiffraction experiment with 2 mm thick sec-
tion of spruce wood embedded in resin: note asym-
metry of patterns in enlargement (far left) which can
be used to determine local orientation of cellulose
fibrils in cell wall (arrows); arrows are plotted in right
image with convention that they represent projection
of vector parallel to fibrils onto plane of cross-
section; picture clearly shows that all cells are right
handed helices. Reprinted with permission from
Ref. 63, 2003, Elsevier Science
7

27 a cell size versus cell density and b cell wall thick-
ness d versus cell size for PCCN systems: for com-
parison, here it is shown other nanocomposite foams
obtained by series of recent studies;64,69 PP: polypro-
pylene based, PLA: polylactide based nanocomposite
foams
Recently, some literature has also been available7073
related to the reactive extrusion foaming of various
nanocomposites.
Electrospining processing
Fibres and nanofibres of N6CN (diameter of 100
500 nm) were electrospun from 1,1,1,3,3,3-hexafluoro-2-
propanole (HFIP) solution and collected as non-woven
fabrics or as aligned yarns.74 The electrospinning
process resulted in highly aligned MMT particles and
nylon 6 crystallites. The cylindrical shaped fibres and
nanofibres, ribbon shaped fibres were also found in the
products (Fig. 28). The electrospinning can be expected
to align other nanofillers such as carbon nanotubes.
Porous ceramic materials via PLSNCs
Very recently, a new route for the preparation of porous
ceramic material from thermosetting epoxy/clay nano-
composite was first demonstrated by Brown et al.75 This
route offers attractive potential for diversification and
application of the PPCNs. Ray and co-workers have
reported the results on the novel porous ceramic
material via burning of the PLA/LS system (PLACN)
which contains 3.0 wt-% inorganic clay.76 The SEM
image of fracture surface of porous ceramic material
Okamoto Recent advances in polymer/layered silicate nanocomposites
28 Micrograph (TEM) of ribbon shaped nanofibre.
Reprinted with permission from Ref. 74, 2002,
Elsevier Science
prepared from simple burning of the PLACN in a
furnace up to 950uC is shown in Fig. 29. After complete
burning, as seen in Fig. 29, the PLACN becomes white
mass with porous structure. The bright lines in the SEM
image correspond to the edge of the stacked silicate
layers. In the porous ceramic material, the silicate layers
form a cards house structure, which consist of the large
plates with length of ,1000 nm and thickness of about
3060 nm. This implies that the further stacked platelet
structure is formed during burning. The material
exhibits the open cell type structure with 1001000 nm
diameter void, the BET surface area of 31 m2 g21 and a
low density of porous material of 0.187 g mL21
estimated by the buoyancy method. The BET surface
area value of MMT is 780 m2 g21 and that of the porous
ceramic material is 31 m2 g21, suggesting that
y25 MMT plates were stacked together. When MMT
is heated .700uC (but ,960uC), first all OH groups are
eliminated from the structure, and thus MMT is
decomposed into that of a non-hydrated aluminosilicate.
This transformation radically disturbs the crystalline
network of the MMT, and resulting diffraction pattern
29 Image (SEM) of porous ceramic material after coated
with platinum layer (,10 nm thickness). Reprinted
with permission from Ref. 76, 2002, American
Chemical Society
Materials Science and Technology 2006 VOL 22 NO 7 771
Okamoto Recent advances in polymer/layered silicate nanocomposites

is indeed often typical of an amorphous (or non-

crystalline) phase. The estimated rough value of
compression modulus K is in the order of ,1.2 MPa,
which is five orders of magnitude lower than the bulk
modulus of MMT (,102 GPa).2 In the stressstrain
curve, the linear deformation behaviour is nicely
described in the early stage of the deformation, i.e. the
deformation of the material closely resembles that of
ordinary polymeric foams.77 This open cell type porous
ceramic material consisting of the cards house structure
is expected to provide the strain recovery and excellent
energy dissipation mechanism after unloading in the
elastic region up to 8% strain, probably each plate bend
like leaf spring. This porous ceramic material is a new
material possessing feature of elastic and very light-
weight. This new route for the preparation of porous
ceramic material via burning of nanocomposites can be
expected to pave the way for much broader range of
applications of the PLSNCs. This porous ceramic
material closely relates an excellent insulator property
for flame reterdant of PLSNCs.2 The flame behaviour
must derive from the morphological control of the
shielding properties of the graphitic/clay created during
polymer ablation.

Physicochemical phenomena
Biodegradability
Another most interesting and exciting aspect of nano-
composite technology is the significant improvements
of biodegradability of biodegradable polymers after
nanocomposites preparation with organoclay. Aliphatic
polyesters are among the most promising materials for
the production of environmentally friendly biodegrad-
able plastics. Biodegradation of aliphatic polyester is
well known, in that some bacteria degrade them by
producing enzymes, which attack the polymer. Tetto
and his colleagues78 first reported some results about the
biodegradability of nanocomposites based on PCL, in
which the authors found that the poly(e-caprolactone)
(PCL)/LS nanocomposites showed improved biodegrad-
ability compared with pure PCL. According to them, the
improved biodegradability of PCL after nanocomposites
formation may be due to the catalytic role of the
organoclay in the biodegradation mechanism. However,
still it is unclear how the clay increases the biodegrada-
tion rate of PCL.
Recently, Lee et al.79 reported the biodegradation
of aliphatic polyester based nanocomposites under
compost. Figure 30a and b represents the clay content
dependence of biodegradation of aliphatic polyester
(APES) based nanocomposites prepared with two
different types of clays respectively. It is assumed that
the retardation of biodegradation owing to the improve-
ment of the barrier properties of the aliphatic APSE
after nanocomposites preparation with clay. However,
there are no data about permeability.
Very recently, Yamada and Okamoto et al.8083 first
reported the biodegradability of neat PLA and corre-
sponding nanocomposites prepared with trimethyl
octadecylammonium modified MMT (3C1C18-MMT)
with details mechanism. The used compost was prepared
from food waste, and tests were carried out at a
temperature of 582uC. Figure 31a shows the real
picture of the recovered samples of neat PLA and
30 Biodegradability of APES nanocomposites with a
Closite 30B and b Closite 10A. Reprinted with permis-
sion from Ref. 79, 2002, Elsevier Science
PLACN4 (3C1C18-MMT54 wt%) from compost with
time. The decreased molecular weight Mw and residual
weight percentage Rw of the initial test samples with time
were also reported in Figure 31b. The biodegradability
of neat PLA is significantly enhanced after PLSNC
preparation. Within one month, both extent of Mw and
extent of weight loss are almost the same level for both
PLA and PLACN4. However, after one month, a sharp
change occurs in weight loss of PLACN4, and within
two months, it is completely degrade in compost. The
degradation of PLA in compost is a complex process
involving four main phenomena, namely
(i) water absorption
(ii) ester cleavage and formation of oligomer fragments
(iii) solubilisation of oligomer fragments
(iv) diffusion of soluble oligomers by bacteria.84
Therefore, the factor, which increases the hydrolysis
tendency of PLA, ultimately controls the degradation of
PLA. It is expected that the presence of terminal
hydroxylated edge groups of the silicate layers may be
one of the responsible factors for this behaviour. In the
case of PLACN4, the stacked (about four layers) and
intercalated silicate layers are homogeneously dispersed
in the PLA matrix (from TEM image)82 ,and these
hydroxy groups start heterogeneous hydrolysis of the
PLA matrix after absorbing water from compost. It
takes some time to start this process. For this reason, the
weight loss and degree of hydrolysis of PLA and
PLACN4 are almost the same up to one month (see
Fig. 31b). However, after one month, there is a sharp
weight loss in the case of PLACN4 compared with that
of PLA. That means one month is a critical value to
start heterogeneous hydrolysis, and owing to this type of
hydrolysis matrix becomes very small fragments and

772 Materials Science and Technology 2006 VOL 22 NO 7

 Okamoto Recent advances in polymer/layered silicate nanocomposites

31 a real picture of biodegradability of neat PLA and PLACN4 recovered from compost with time: nitial shape of crys-
tallised samples was 361060.1 cm3 and b time dependence of residual weight Rw and of matrix Mw of PLA and
PLACN4 under compost at 582uC. Reprinted with permission from Ref. 80, 2002, American Chemical Society

disappears with compost. This assumption was con-
firmed by conducting the same type of experiment with
PLACN prepared by dimethyl dioctdecyl ammonium
salt modified synthetic mica which has no terminal
hydroxylated edge group, and the degradation tendency
almost the same with neat PLA.81
They also conducted respirometric test to study
degradation of the PLA matrix in compost environment
at 582uC. For this test the used compost was made
from bean curd refuse, food waste and cattle feces. Unlike
weight loss, which reflects the structural changes in
the test sample, CO2 evolution provides an indicator of
the ultimate biodegradability of PLA in PLACN4
(prepared with (N(cocoalkyl)N,N-[bis(2-hydroxyethyl)]-
N-methylammonium modified synthetic mica,), i.e.
mineralisation, of the samples. Figure 32 shows the time
dependence of the degree of biodegradation of neat PLA
and PLACN4, indicating that the biodegradability of
PLA in PLACN4 is enhanced significantly. The presence
of organoclay may thus cause a different mode of attack
on the PLA component, which might be due to the
presence of hydroxy groups. Details of the mechanism of
biodegradability are presented in relevant literature.81,82
K. Okamoto and M. Okamoto also investigated
biodegradability of neat PBS before and after
nanocomposites preparation with three different
types of organoclay. They used alkylammonium or
alkylphosphonium salts for the modification of pristine
layered silicates, and these surfactants were toxic for
microorganisms.43,85
Figure 33a shows the real pictures of recovered
samples of neat PBS and various nanocomposites from
the compost after 35 days. From Fig. 33, it is clearly
observed that many cracks appeared in nanocomposite
samples compared with that of neat PBS. This observa-
tion indicates the improved degradability of nanocom-
posites in compost. This kind of fracture has an
advantage for biodegradation because of easy to mix
with compost and to create much more surface area for
further attack by micro-organisms, and it should be
noted here that the extent of fragmentation is directly
related to the nature of organoclay used for nanocom-
posites preparation. They also conducted the gel
permeation chromatography (GPC) measurement of
recovered samples from compost, and it can be found
that the extent of molecular weight loss is almost the

Materials Science and Technology 2006 VOL 22 NO 7 773

Okamoto Recent advances in polymer/layered silicate nanocomposites

32 a degree of biodegradation (i.e. CO2 evolution) and b time dependent change of matrix Mw of neat PLA and PLACN4
(MEE clay 54 wt-%) under compost at 582uC. Reprinted with permission from Ref. 81, 2004, WILEY-VCH Verlag
GmbH & Co

33 Biodegradability of neat PBS and various nanocomposites sheets a under compost and b under soil field. Reprinted
with permission from Ref. 85, 2003, John Wiley & Sons

same for all samples (see Table 5). This result indicates
that the extent of hydrolysis of PBS in pure state or
organically modified layered silicate (OMLS) filled
systems is the same in compost.
Except for the PBS/qC16-SAP (n-hexadecyl tri-n-butyl
phosphonium cation modified saponite) system, the
degree of degradation is not different for other samples.
This observation indicates that MMT or alkylammo-
nium cations, and other properties have no effect on the
biodegradability of PBS at the same time. The acceler-
ated degradation of PBS matrix in the presence of qC16-
SAP may be due to the presence of alkylphosphonium
surfactant. This kind of behaviour is also observed in the
case of PLA/LS nanocomposite systems.
They also observed the nature of degradation of PBS
and various nanocomposites under soil field. The
present experiment was conducted for one, two and six
months. After one and two months, there is no change
on the nature of surface of the samples, but after six
months black or red spots appeared on the surface of
nanocomposites samples. Figure 33b represents the
results of degradation of neat PBS and various
nanocomposites sheets recovered from soil field after
six months. It is reported that these spots on the sample
surface are due to the fungus attacked, because when
these parts were put into the slurry and a clear growth of
fungus was observed. These results also indicate that
nanocomposites exhibit the same or higher level of
biodegradability compared with PBS matrix.
Photodegradation
Very recently, Hiroi and Okamoto et al.86 first reported
the photodegradability of neat PLA and corresponding

Table 5 Results of various samples recovered from compost after 35 days with GPC measurement

Samples Mw, 61023 g mol21 Mn, 61023 g mol21 M ow *, 61023 g mol21 Mw/M ow

PBS 16 3.8 101 0.16

PBS/C18-MMT 17 6.6 104 0.16
PBS/qC18-MMT 17 4.4 112 0.15
PBS/qC16-SAP 8.7 1.2 91 0.096
*Molecular weight before composting.

774 Materials Science and Technology 2006 VOL 22 NO 7

 Okamoto Recent advances in polymer/layered silicate nanocomposites

34 UV/VIS transmission spectra of neat PLA and nano-

composite (PLANC1.7). Reprinted with permission
35 Hole fraction versus temperature for N6 based nano-
from Ref. 86, 2004, WILEY-VCH Verlag GmbH & Co
compopsite. Reprinted with permission from Ref. 88,
2001, VSP
PLA nanocomposite prepared by organically modified
layered titanate as a new nanofiller. One of the features
immobilised. This loss of mobility translates in their
of this material is photocatalytic reactivity, such as
model into a free volume loss. The effect was simulated
titania (TiO2). The photocatalytic reaction of anatase-
by a large adhesion ratio e*12/e*11(5313.54 kJ mol21/
TiO2, such as evolution of hydrogen gas from water or
32.09 kJ mol21), which is the energetic interaction
oxidative degradation of organic compounds, has
parameter between polymer clay and polymer polymer.
attracted intense research interest because of their
It is also reported the value of the free volume reduction
possible application to the conversion of solar energy
for the polystyrene based nanocomposite system.89 In
into chemical energy.87
the case of 4 wt-% organoclay loading, the reducton is
Figure 34 shows the UV/VIS transmission spectra of
much lower (46%) than that of N6 based nanocompo-
pure PLA and nanocomposite (PLANC1.7). The spectra
sites owing to the weak interaction between polymer and
show that the VIS region (larger than ,400 nm) is
silicate surfaces.
changed with increasing absorbency by the presence of
Recently, some literatures are also available90 related
titanate layers compared with neat PLA. For UV
to the PVT dependencies of commercial PP melt and its
wavelengths, there is strong absorption up to 320 nm,
nanocomposites including small amount of a compati-
resulting in 0% transmittance. This significant change in
biliser. Another recent approach is positron annihilation
the spectra may indicate that occurrence of the photo-
lifetime spectroscopy for evaluation of the free volume
degradation of PLA matrix. To confirm this, they
fraction in PLSNCs.91
conducted some preliminary experiments on photode-
gradation of PLANCs under sunshine weathermeter at
60uC. After 300 h, there was no change in the nature of Computer simulation
sample surfaces of neat PLA, however, the surface Theoretical phase diagram of PLSNCs
colour of nanocomposite samples altered yellow and/or
Recently, Ginzburg and Balazs developed simple models
light brown. Table 6 shows the GPC measurement of
that describe the liquid crystalline ordering in the
recovered samples from the test. The drop in Mw
polymer platelet systems.9295 They combined a density
accompanied with broadening of Mw/Mn indicates that
functional theory (DFT) with a selfconsistent field
the enhancement of degradation of PLA in the titanate
(SCF) model to calculate the phase behaviour of thin,
filled system has occurred.
oblate colloidal particles that are coated with surfactants
and dispersed in a polymer melt. These coated particles
Pressure volume temperature (PVT) behaviour
represent organoclay sheets. By intergrafting the two
Recently, in N6 based nanocomposites (N6CNs) the methods, they investigated the effect of the surfactants
reduction in free volume by 1217% was reported characteristics (grafting density rgr and length Ngr) and
through a pioneering effort by Utracki et al.88 the polymer intercalant interaction energy on the
Figure 35 shows the temperature dependence of the free polymer/clay phase diagram (see Fig. 36).93 Depending
volume reduction by the addition of nanoclay particles. on the values of these critical parameters and clay
It is speculated that the N6 chains are absorbed on the volume fraction w, the system can be in an isotropic or
solid clay surface and the first few absorbed layers are nematic phase (exfoliated system). The system can also
form a smectic, crystal, columnar, or house of cards
Table 6 Results of sample recovered from weathermeter
plastic solid as well as a two phase immiscible mixture.
after 300 h with GPC measurement86
Using this model they isolated conditions that lead to
Samples Mw, 61023 g mol21 Mw/Mn Mw/M ow the stabilisation of the exfoliated nanocomposite system
and to the narrowing of the immiscible two phase
PLA 198 1.53 0.94 regions.
PLANC1.7 93.7 1.89 0.68 Furthermore, they extended their study to take
PLANC3.9 86.3 1.86 0.76
end functionalised polymer chains into consideration.94
M ow : molecular weight before test. The parameter e characterises the interaction between

Materials Science and Technology 2006 VOL 22 NO 7 775

Okamoto Recent advances in polymer/layered silicate nanocomposites

a isotropic (I); b nematic (N); c smectic (S); d columnar (Col); e plastic solid (house of cards) (PS); f crystal (Cr)
36 Mesophases of oblate uniaxial particles dispersed in polymer: nematic director n in ordered phases is aligned along
Z axis, disks lie in XY plane; broken lines show smectic layers and columns. Reprinted with permission from
Ref. 94, 2000, American Chemical Society

the terminal functional group and the surface. For
small negative e, the system is completely immiscible.
As the sticker/surface attraction is increased, the
system exhibits isotropic and nematic morphologies at
relatively low clay volume fractions (w,0.12). The
latter structures correspond to thermodynamically
stable, exfoliated nanocomposite. Finally, when the
surface/sticker attraction is increased even further, the
system exhibits a plastic solid at low w, and a columnar
phase at very high w (see Fig. 37). The resulting
phase diagrams can be used as guidelines for the
nanocomposite formation with thermodynamically
stable morphologies.
Atomic scale structure and binding energy in
PLSNCs
Molecular simulation techniques are used to explore and
characterise the atomic scale structure, and to predict
binding energies and basal spacing of PLSNCs based on
PP and PPMA, MMT and different alkylammonium
ions as intercalants.96 The basic machinery of the
procedure consists in building a molecular model
comprising PP, a given intercalant and MMT, refining
and equilibrating it by molecular mechanics/molecular
dynamics (MM/MD), and calculating the binding
energies as guidelines for screening among different

776 Materials Science and Technology 2006 VOL 22 NO 7

 Okamoto Recent advances in polymer/layered silicate nanocomposites

37 Phase diagram for polymer/clay mixture: here e is

sticker clay adhesion energy. Reprinted with permis-
sion from Ref. 94, 2000, WILEY-VCH Verlag GmbH
& Co
intercalants to make PLSNCs characterised by strong
interface between dispersed clay platelets and the PP
matrix (see Fig. 38). Figure 39 shows the predicted
binding energy versus volume of the intercalant. From a
global interpretation of all these molecular dynamics
simulation results, it can be concluded that intercalants
with smaller volume are more effective for clay
modification as they improve the thermodynamics of
the system by increasing the binding energy, while on the
other hand intercalants with longer tails are more
effective for intercalation and exfoliation processes, as
they lead to higher basal spacing. Alike, for a given
surfactant molecule, the use of PPMA in the prepara-
tion of PLSNCs results in a system with the most
favourable interaction energy but with a lower basal
spacing. Under the hypothesis, the MMT platelets are
: Ebind (PPMA/intercalant); m: Ebind (PPMA/MMT).
39 Predicted binding energy versus volume of interca-
lant. Reprinted with permission from Ref. 96, 2004,
Elsevier Science
uniformly dispersed in a polymer matrix, the PPMA
yields higher interfacial strength with clay than neat PP.
The use of neat PP and intercalants with higher
molecular volume offers the higher values of the basal
spacing and thus, in principle, they should be more
effective in the exfoliation process.
Recently, some literatures are also available97100
related to the confined polymer chains into the silicate
galleries by coarse grained MD simulation.
Future prospects of PLSNCs
Development of the PLSNCs is one of the latest
evolutionary steps of the polymer technology. The

38 Three component model used for basal spacing simulations, consisting of two layers of MMT with Kz cations (stick
model), a four molecules of trimethylammonium cation or b dimethylstearylammonium cation (stick and ball model),
and one molecule of PPMA (ball model). Reprinted with permission from Ref. 96, 2004, Elsevier Science

Materials Science and Technology 2006 VOL 22 NO 7 777

Okamoto Recent advances in polymer/layered silicate nanocomposites

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